CN109937236A - Rubber composition for tire and tire - Google Patents
Rubber composition for tire and tire Download PDFInfo
- Publication number
- CN109937236A CN109937236A CN201780070425.1A CN201780070425A CN109937236A CN 109937236 A CN109937236 A CN 109937236A CN 201780070425 A CN201780070425 A CN 201780070425A CN 109937236 A CN109937236 A CN 109937236A
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- CN
- China
- Prior art keywords
- scattering
- rubber
- rubber composition
- tire
- correlation length
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 101
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 238000004458 analytical method Methods 0.000 claims abstract description 37
- 229920003049 isoprene rubber Polymers 0.000 claims abstract description 31
- 238000001956 neutron scattering Methods 0.000 claims abstract description 16
- 238000000333 X-ray scattering Methods 0.000 claims abstract description 9
- 239000011903 deuterated solvents Substances 0.000 claims abstract description 6
- 238000000235 small-angle X-ray scattering Methods 0.000 claims description 14
- 238000004898 kneading Methods 0.000 description 65
- 238000004073 vulcanization Methods 0.000 description 40
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- 239000005864 Sulphur Substances 0.000 description 16
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- 239000000391 magnesium silicate Substances 0.000 description 2
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- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- CUXVCONCZJJRCS-UHFFFAOYSA-N nitrosilane Chemical compound [O-][N+]([SiH3])=O CUXVCONCZJJRCS-UHFFFAOYSA-N 0.000 description 1
- 235000019488 nut oil Nutrition 0.000 description 1
- 239000010466 nut oil Substances 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229940043266 rosin Drugs 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000001998 small-angle neutron scattering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- YOEWQQVKRJEPAE-UHFFFAOYSA-L succinylcholine chloride (anhydrous) Chemical class [Cl-].[Cl-].C[N+](C)(C)CCOC(=O)CCC(=O)OCC[N+](C)(C)C YOEWQQVKRJEPAE-UHFFFAOYSA-L 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- FPBXRRDHCADTAL-UHFFFAOYSA-N triethoxy(3-nitropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC[N+]([O-])=O FPBXRRDHCADTAL-UHFFFAOYSA-N 0.000 description 1
- FJXRKYLOOJTENP-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyldisulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSCC[Si](OCC)(OCC)OCC FJXRKYLOOJTENP-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical class CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- URIYERBJSDIUTC-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltrisulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSCC[Si](OCC)(OCC)OCC URIYERBJSDIUTC-UHFFFAOYSA-N 0.000 description 1
- QPPXVBLDIDEHBA-UHFFFAOYSA-N trimethoxy(3-nitropropyl)silane Chemical compound CO[Si](OC)(OC)CCC[N+]([O-])=O QPPXVBLDIDEHBA-UHFFFAOYSA-N 0.000 description 1
- BNBXBRPOAJZBNB-UHFFFAOYSA-N trimethoxy-[4-(4-trimethoxysilylbutyldisulfanyl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCSSCCCC[Si](OC)(OC)OC BNBXBRPOAJZBNB-UHFFFAOYSA-N 0.000 description 1
- GSZUEPNJCPXEGU-UHFFFAOYSA-N trimethoxy-[4-(4-trimethoxysilylbutyltrisulfanyl)butyl]silane Chemical class CO[Si](OC)(OC)CCCCSSSCCCC[Si](OC)(OC)OC GSZUEPNJCPXEGU-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0025—Modulus or tan delta
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
A kind of rubber composition for tire is provided, there is low tan δ at about 60 DEG C, and there is excellent energy to failure at about 25 DEG C.A kind of rubber composition for tire is provided, comprising the rubber components containing isoprene rubber, which has 55nm correlation length belowThe correlation lengthBy being determined with the fitting of following formula 1 to 6 by the scattering strength curve I (q) that X-ray scattering analysis or neutron scattering analysis obtain:ξ < Ξb< Ξc(formula 2) A=8 π Naσ2ξ3(formula 3) A, B, C, ξ,: fitting parameter q: Scattering of Vector Na: per unit volume number (a/cm of the scatterer with correlation length ξ3)Nb: there is correlation lengthScatterer per unit volume number (a/cm3)Nc: there is correlation lengthScatterer per unit volume number (a/cm3) σ: the poor (electronics (cm of electron density between scatterer and surrounding substrate‑3)) or scatterer and surrounding deuterated solvent between scattering length density contrast (cm‑2) θ: angle of scattering λ: the wavelength of X-ray or neutron.
Description
Technical field
The present invention relates to rubber composition for tire and tires.
Background technique
With the trend recently due to controlling CO2 emission caused by the growing interest to environmental problem, to fuel
The demand of economy automobile is increasing always.This generates the further demands to the tire with reduced rolling resistance.
The cross-linked structure of known rubber composition for tire is related to its physical property.It therefore, it has been developed to various use
In the technology (for example, patent document 1 and non-patent literature 1) of analysis cross-linked structure.For example, patent document 1, which reports, to be had
The rubber composition of even cross-linked structure shows lower energy loss；However, providing homogeneous cross-link structure without sufficiently studying
Method.
Reference listing
Patent document
5658219 B of patent document 1:JP
Non-patent literature
Non-patent literature 1:Yuko Ikeda etc., vulcanization: the new concern by low-angle neutron scattering to traditional technology
(Vulcanization:New Focus on a Traditional Technology by Small-Angle Neutron
Scattering),Macromolecules 2009,42,2741-2748.
Summary of the invention
Technical problem
The present inventor's studies have shown that by control cross-linked structure, can improve simultaneously tan δ at about 60 DEG C and
Energy to failure at about 25 DEG C (by the way that fracture tensile strength is multiplied the quotient obtained again divided by 2 with elongation at break).
The purpose of the present invention is to provide a kind of rubber composition for tire, have low tan δ at about 60 DEG C, and
There is excellent energy to failure at about 25 DEG C.
Technological means
For realize the target and carried out a large amount of effort the result is that the inventors discovered that, when containing isoprene rubber
Rubber composition be controlled as with correlation length ΞbWhen reduced cross-linked structure, the tire comprising crosslinked rubber composition can
To realize the abundant abundant improvement reduced with fracture property of energy loss, wherein by passing through X-ray with the fitting of following formula 1 to 6
In the scattering strength curve I (q) that scattering analysis or neutron scattering analysis obtain, to determine correlation length Ξb.It is complete based on the discovery
At the present invention.
Specifically, rubber composition for tire of the invention contains the rubber components comprising isoprene rubber, and have
There is 55nm correlation length Ξ belowb, the correlation length ΞbBy passing through X-ray scattering analysis or neutron with the fitting of following formula 1 to 6
Scattering analysis obtain scattering strength curve I (q) and determine:
ξ < Ξb< Ξc(formula 2)
A=8 π Naσ2ξ3(formula 3)
A, B, C, ξ, Ξb, Ξc: fitting parameter
Q: Scattering of Vector
Na: per unit volume number (a/cm of the scatterer with correlation length ξ3)
Nb: there is correlation length ΞbScatterer per unit volume number (a/cm3)
Nc: there is correlation length ΞcScatterer per unit volume number (a/cm3)
σ: the poor (electronics (cm of electron density between scatterer and surrounding substrate-3)) or scatterer and surrounding deuterated solvent it
Between scattering length density contrast (cm-2)
θ: angle of scattering
λ: the wavelength of X-ray or neutron
Preferably, X-ray scattering analysis is small angle x-ray scattering (SAXS) analysis, and neutron scattering analysis is in low-angle
Sub- scattering analysis.
Preferably, the value of the q defined by formula 6 is 10nm-1Below.
Another aspect of the present invention is a kind of tire comprising rubber composition for tire.
Advantageous effect of the invention
Rubber composition of the invention contains isoprene rubber, and has correlation length within a predetermined range
Ξb, the correlation length ΞbPass through the scattering strength obtained with the fitting of formula 1 to 6 by X-ray scattering analysis or neutron scattering analysis
Curve I (q) and determine.This rubber composition for tire has low tan δ at about 60 DEG C, and with excellent at about 25 DEG C
Different energy to failure.
Detailed description of the invention
Fig. 1 shows the exemplary scattering strength curve obtained by SANS analysis.
Specific embodiment
Rubber composition for tire of the invention contains the rubber components comprising isoprene rubber, and has 55nm
Correlation length Ξ belowb, the correlation length ΞbBy being analyzed with the fitting of formula 1 to 6 by X-ray scattering analysis or neutron scattering
The scattering strength curve I (q) (for example, Fig. 1) of acquisition and determine.
In the fitting parameter obtained by curve matching, thus it is speculated that the correlation length ξ in 1nm to 100 μ ms corresponds to
The distance between crosslinking points in polymer, and speculate the correlation length Ξ in 0.1nm to 100 μ msbCorresponding in polymer not
The size of uniform network.Correlation length Ξ in the range of 0.1nm to 100 μmbIt is considered as the cross-linked structure of rubber composition
Most important factor, and think that the low tan δ at about 60 DEG C and the height at about 25 DEG C may be implemented by controlling the parameter
Energy to failure.
Correlation length Ξ in the present inventionbIt is in thickness is about 1mm, length is about 16mm, and width is about on the plaques of 16mm
Measurement.It, can be from this plaques that tyre element (such as tire curing tyre surface) is cut for tire sample
It measures.
Curve matching is carried out by least square method.
In the present invention, by controlling correlation length ΞbFor 55nm hereinafter, the low tan at about 60 DEG C can be obtained simultaneously
δ and the high energy to failure at about 25 DEG C.In order to further decrease the tan δ at about 60 DEG C, and further increased simultaneously about
Energy to failure at 25 DEG C, correlation length ΞbPreferably 35nm hereinafter, more preferably 25nm hereinafter, particularly preferably 15nm or less.Ξ
The lower limit of b is not particularly critical, and preferably as small as possible.
X-ray scattering analysis can be suitably small angle x-ray scattering (SAXS) (SAXS) analysis (angle of scattering: usual 10 degree with
Under), wherein can be with x-ray bombardment polymer material to measure scattering strength.
In small angle x-ray scattering (SAXS) analysis, can by measure by the scattered x-ray that is generated with x-ray bombardment substance with
The X-ray of small angle of scattering scattering, to obtain the structural information of substance.In this way it is possible to analyze the orderly of several nanometer scales
Structure, such as the micro phase separation structure of polymer material.
In order to obtain detailed molecular structure information, SAXS analysis should be able to measure the scattering of the X-ray with high S/N ratio
It is linear.Therefore, preferably have at least 10 from the X-ray that synchrotron emits10(photon/s/mrad2/mm2/ 0.1%bw)
Brightness.
Symbol bw indicates the bandwidth of the X-ray emitted from synchrotron.The example of this synchrotron includes belonging to financial group
The light beam line BL03XU of the large-scale synchrotron light device " SPring-8 " of the high luminance light research establishment of legal person and
BL20XU。
Term " S/N ratio " is the abbreviation that " signal/noise ratio " is calculated and by signal variance divided by noise variance.
Brightness (the photon/s/mrad of X-ray2/mm2/ 0.1%bw) it is preferably 1010More than, more preferably 1012More than.On
Limit is not that particularly critical but used X-ray intensity is preferably sufficiently low without causing radiation injury.
Number of photons (number of photons/s) in X-ray is preferably 107More than, more preferably 109More than.The upper limit is not especially to close
Key, but X-ray intensity used is preferably sufficiently low without causing radiation injury.
Neutron scattering analysis can be suitably low-angle neutron scattering (SANS) analysis (angle of scattering: usual 10 degree with
Under), wherein polymer material can be with neutron exposure to measure scattering strength.
In low-angle neutron scattering analysis, can by measure by the scattered neutron that is generated with neutron exposure substance with small scattered
The neutron of firing angle scattering, to obtain the structural information of substance.In this way it is possible to the ordered structure of several nanometer scales is analyzed,
Such as the micro phase separation structure of polymer material.
SANS analysis can be related to the known technology based on magnetic structure or deuterate technology.When using deuterate technology, for example,
Polymer material can be swollen in deuterated solvent, and the polymer material balanced in deuterated solvent can use neutron exposure
To measure scattering strength.The example of this deuterated solvent for swollen polymer material includes heavy water, deuterated hexane, deuterated first
Benzene, deuterated chloroform, deuterated methanol, deuterated DMSO ((D3C)2S=O), deuterated tetrahydrofuran, deuterated acetonitrile, deuterated dichloromethane,
Deuterated benzene and deuterated n,N-Dimethylformamide.
It can be studied from independent administrative corporation's Japan Atomic is for example belonged to for the neutron scattering analysis such as neutron of SANS
The SANS-J light beam line of the JRR-3 research reactor of Development institution obtains.
In the same manner as SAXS analysis, the flux density (neutron/cm of neutron2/ s) it is preferably 103More than, more preferably 104With
On, have the neutron scattering of high S/N ratio linear to obtain.The upper limit be not it is particularly critical, used netron-flux density is preferred
It is sufficiently low without causing radiation injury.
It is excellent due to needing to measure the finer molecular structure of polymer material in X-ray or neutron scattering analysis
The value for being selected in the q defined by formula 6 is 10nm-1It is analyzed under the conditions of below.The range of q is more preferably 20nm-1Hereinafter, because
The information of more fritter is desirably resulted in for bigger numerical value.
The X-ray scattered in SAXS analysis can be detected by X-ray detector, may then pass through for example, by using next
Image is generated from the image processor of the X-ray detection data of X-ray detector.
The example of X-ray detector includes two-dimensional detector, as X-ray film, nuclear emulsion plate, radioscopic image pickup tube,
X-ray fluorescence amplifier, X-ray image intensifier, X-ray imaging plate, X-ray CCD and X-ray non-crystalline material detector；With
Line sensor one-dimensional detector.It can suitably be selected according to the type or condition or other factors of polymer material to be analyzed
Select X-ray detector.
Image processor can suitably can be based on the X-ray detection data from X-ray detector and generate X-ray
The common image processor of dispersion image.
SANS analysis can also be carried out based on identical principle is analyzed with SAXS；It can be detected and be scattered by neutron detector
Neutron, may then pass through the image processor for example, by using the neutron detection data from neutron detector to generate figure
Picture.Similar to the abovely, neutron detector can be known two-dimensional detector or one-dimensional detector, and image processor can
To be the known neutron detector that can generate neutron scattering image.These equipment can be properly selected.
Rubber composition of the invention contains isoprene rubber.The example of isoprene rubber includes natural rubber
(NR), synthetic polyisoprenes rubber (IR), obtained by modified NR or IR modification NR or IR, by partly or complete from NR
The copolymer and liquid IR for refining NR, isoprene and other monomers for removing phosphatide and protein entirely and obtaining.These
Isoprene rubber can be used alone, and can also be applied in combination two or more.Other than isoprene rubber,
Rubber composition of the invention can also contain the other materials that can be used for tire art.
For example, the rubber components of rubber composition of the invention may include other rubbers in addition to isoprene rubber
Glue.Other preferred rubber are the rubber that 3 grades of stable free radicals can be generated as isoprene rubber.It can also make
With the rubber that cannot generate 3 grades of free radicals, such as styrene butadiene ribber (SBR) and polybutadiene rubber (BR).It can also be with
Use butyl system rubber.
If SBR can be common any SBR in tire industry using SBR.Example includes the styrene of emulsion polymerization
The styrene butadiene ribber (S-SBR) of butadiene rubber (E-SBR) and polymerisation in solution.
If BR can be common any BR in tire industry using BR.Example includes high-cis BR, such as can be from Japan
The BR 1220 that Rui Weng Co., Ltd. the obtains and BR130B and BR150B that can be obtained from Ube Industries, Ltd, and contain
The BR of syndiotactic polybutadiene crystal, the VCR412 and VCR617 that can be such as obtained from Ube Industries, Ltd.
If butyl system rubber can be common any butyl rubber in tire industry using butyl system rubber.Example
Including butyl rubber (IIR) and halogenated butyl rubber (X-IIR), such as brombutyl (Br-IIR) and chlorinated scoline
(Cl-IIR)。
In order to promote to be formed cross-linked structure more evenly, with the rubber components in rubber composition of the invention for 100 matter
% meter is measured, the amount of isoprene rubber is preferably at least 1 mass % or at least 20 mass %, more preferably at least 50 mass %
Or at least 70 mass %, still more preferably at least 90 mass %, and can be 100 mass %.Except isoprene rubber with
The amount of other outer each rubber preferably at most 99 mass % or at most 80 mass %, more preferably up to 50 mass %, Huo Zhezhi
More 30 mass % even more preferably from most 10 mass %, and can be 0 mass %.
For example, rubber composition of the invention can contain carbon black.Common any carbon black in tire industry can be used.It is real
Example includes N134, N110, N220, N234, N219, N339, N330, N326, N351, N550 and N762.Relative to 100 mass parts
Rubber components, the amount of carbon black (if you are using) is preferably at least 1 mass parts or at least 15 mass parts, more preferably at least
30 mass parts, but preferably at most 100 mass parts, more preferably up to 80 mass parts.
Rubber composition of the invention can contain such as silica.Common any dioxy in tire industry can be used
SiClx.Example includes dry silica (anhydride silica) and wet silica (aqueous silicon dioxide).Relative to 100
The rubber components of mass parts, the amount of silica (if you are using) are preferably at least 1 mass parts or at least 15 mass parts, more
Preferably at least 30 mass parts, but preferably at most 200 mass parts, more preferably up to 150 mass parts.
When rubber composition contains silica, it can also contain silane coupling agent.It can be used commonly used in wheel
Any silane coupling agent of tire industry.Example includes sulfidesilane coupling agent, such as bis- (3- triethoxysilyls third
Base) tetrasulfide, bis- (2- triethoxysilylethyl) tetrasulfides, bis- (4- triethoxysilyl butyl) four sulphur
It is compound, bis- (3- trimethoxy-silylpropyl) tetrasulfides, bis- (2- trimethoxysilylethylgroup group) tetrasulfides, double
(2- triethoxysilylethyl) trisulfide, bis- (4- trimethoxysilyl butyl) trisulfides, bis- (tri- second of 3-
Oxygroup silylpropyl) disulphide, bis- (2- triethoxysilylethyl) disulphide, bis- (4- triethoxy first
Silylation butyl) disulphide, bis- (3- trimethoxy-silylpropyl) disulphide, bis- (2- trimethoxysilyls
Ethyl) disulphide, bis- (4- trimethoxysilyl butyl) disulphide, 3- trimethoxy-silylpropyl-N, N-
Dimethylthiocarbamoyl tetrasulfide, 2- triethoxysilylethyl-N, N- dimethylthiocarbamoyl
Tetrasulfide and 3- triethoxysilylpropyltetrasulfide methacrylate monosulfide；Mercaptosilane coupling agents, such as 3- mercapto
Base propyl trimethoxy silicane, 2- mercaptoethyl triethoxysilane and can from figure advanced in years (Momentive) obtain NXT and
NXT-Z；Vinyl silicane coupling agent, such as vinyltriethoxysilane and vinyltrimethoxysilane；Amino silane is even
Join agent, such as 3-aminopropyltriethoxysilane and 3- TSL 8330；Glycidol ether oxysilane is even
Join agent, such as γ-glycidyl ether oxypropyltriethoxysilane and γ-glycydoxy trimethoxy silicon
Alkane；Nitro silane coupling agent, such as 3- nitropropyl trimethoxy silane and 3- nitropropyltriethoxysilane；And chloro
Silane coupling agent, such as 3- r-chloropropyl trimethoxyl silane and 3- chloropropyl triethoxysilane.Two relative to 100 mass parts
Silica, the amount of silane coupling agent (if you are using) are preferably 1 mass parts or more, but preferably 15 below the mass.
Common any filler in the tire industry except carbon black and silica can be used, including for example inorganic fill out
Material, such as aluminium hydroxide, talcum, mica, magnesia, magnesium sulfate, titanium white, titanium is black, calcium oxide, calcium hydroxide, oxidation magnalium, glues
Soil, pyrophyllite, bentonite, alumina silicate, magnesium silicate, calcium silicates, calcium aluminosilicate, magnesium silicate, silicon carbide, zirconium and zirconium oxide；And have
Machine filler, such as staple fiber and cellulose nano-fibrous.
Rubber composition of the invention can contain such as resin.Common any resin in tire industry can be used.It is real
Example includes aromatic petroleum resin, terpene resin, dicyclopentadiene (DCPD) resin, coumarone-indene resin, α-methylstyrene tree
Rouge, p-tert-butylphenol acetylene resin and acrylic resin.Relative to the rubber components of 100 mass parts, resin (if use
Words) amount be preferably at least 1 mass parts or at least 15 mass parts, more preferably at least 30 mass parts, but preferably at most 200 matter
Measure part, more preferably up to 150 mass parts.
Rubber composition of the invention can contain such as antioxidant.Common any antioxygen in tire industry can be used
Agent.Example includes: naphthylamine antioxidant, such as phenyl-α-naphthylamine；Diphenylamine Antioxidant, such as octylated diphenylamine
With bis- (α, the α '-dimethyl benzyl) diphenylamines of 4,4'-；P-phenylenediamine antioxidant, such as N- isopropyl-N'- phenyl is to benzene two
Bis- -2- naphthyl p-phenylenediamine of amine, N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine and N, N'-；Quinoline antioxidant is such as
2,2,4 trimethyl 1,2 dihydroquinoline polymer；Single phenol antioxidant, such as 2,6- di-tert-butyl-4-methy phenol and benzene
Vinylation phenol；With it is double -, three-or polyphenol antioxidation agent, such as four [methylene -3- (3', 5'- di-t-butyl -4'- hydroxy benzenes
Base) propionic ester] methane.Relative to the rubber components of 100 mass parts, the amount of antioxidant (if you are using) is preferably 0.1
More than mass parts, more than more preferably 0.5 mass parts, but preferably 5 below the mass, more preferably 3 below the mass.
Rubber composition of the invention can be containing for example oily.Common any oil in tire industry can be used.Example packet
Processing oil is included, such as paraffinic, aromatic process oils and naphthenic；And vegetable oil, such as castor oil, cottonseed oil, linseed
Oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, rosin, pine tar, pine tar, tall oil, corn oil, rice bran oil,
Safflower oil, sesame oil, olive oil, sunflower oil, palm-kernel oil, camellia oil, jojoba oil, macadimia nut oil and tung oil.Relatively
In the rubber components of 100 mass parts, the amount of oily (if you are using) is preferably 1 mass parts or more, but preferably 100 mass parts
Below.
Rubber composition of the invention can contain such as wax.Common any wax in tire industry can be used.Example packet
Paraffin is included, such as paraffin wax and microcrystalline wax；Naturally occurring wax, such as vegetable wax and animal wax；And synthetic wax, as ethylene,
The polymer of propylene or other monomers.Relative to the rubber components of 100 mass parts, the amount of wax (if you are using) is preferably
More than 0.1 mass parts, but preferably 10 below the mass.
Rubber composition of the invention can contain such as processing aid.Common any processing in tire industry can be used
Auxiliary agent.Example includes fatty acid metal salts, fatty acid amide, carboxylic acid amide esters, silica surface activator, aliphatic ester, fat
The mixture and fatty acid metal salts of acid metal salt and carboxylic acid amide esters and the mixture of fatty acid amide.Relative to 100 mass parts
Rubber components, the amount of processing aid (if you are using) is preferably 0.1 mass parts or more, but preferably 10 mass parts with
Under.
Rubber composition of the invention can contain such as sulphur.Relative to the rubber components of 100 mass parts, sulphur is (if used
If) amount be preferably 0.5 mass parts or more, more than more preferably 1.5 mass parts, but preferably 6 below the mass, more preferably
Below the mass for 4.
Rubber composition of the invention can contain such as vulcanization accelerator.Common any sulphur in tire industry can be used
Change promotor.Example includes guanidine vulcanization accelerator, sulfenamide vulcanization accelerator, thiazole vulcanization accelerator, thiuram vulcanization rush
Into agent, dithiocar-bamate vulcanization accelerator, thiourea cure promotor and xanthates vulcanization accelerator.These vulcanizations promote
It can be used alone, can also be used in combination into agent.Wherein preferred sulfenamide vulcanization accelerator, and can make
With following sulfenamide vulcanization accelerator:
N- cyclohexyl -2-[4-morpholinodithio sulfenamide (CZ),
N- aoxidizes diethylidene -2-[4-morpholinodithio sulfenamide (OBS),
N- (tert-butyl) -2-[4-morpholinodithio sulfenamide (TBBS),
N- (tert-butyl) -2-[4-morpholinodithio sulfenimide (TBSI),
N, N- dicyclohexylbenzothiazole -2- sulfenamide (DCBS), and
DIBS N,N diisopropylbenzothiazyl 2 sulfenamide (DIBS).
Relative to the rubber components of 100 mass parts, the amount of vulcanization accelerator (if you are using) be preferably 0.5 mass parts with
On, more than more preferably 1.5 mass parts, it is preferred that below the mass for 6, more preferably 4 below the mass.
Rubber composition of the invention can contain such as zinc oxide.Relative to the rubber components of 100 mass parts, zinc oxide
(if you are using) amount is preferably 1 mass parts or more, more than more preferably 2 mass parts, but preferably 8 below the mass,
More preferably 6 below the mass.
Rubber composition of the invention can contain such as stearic acid.Relative to the rubber components of 100 mass parts, stearic acid
(if you are using) amount is preferably 1 mass parts or more, more than more preferably 2 mass parts, but preferably 8 below the mass,
More preferably 6 below the mass.
Rubber composition of the invention is in tire applications.Rubber composition of the invention is preferred for tire tread.
It can be also used for various tyre elements, for example, sidewall, tread base, tread cushioning layer, clinch triangle rubber, bead apex,
The sidewall enhancing of cushion rubber, body cord rubberizing rubber, insulation rubber, chafer, liner layer and run-flat tire
Layer.Pneumatic tire can be preferably using the tyre type of rubber composition.In addition, rubber composition can also be applied to it is riding
The inflation of vehicle, truck and bus or motorcycle or non-inflatable tyre.
Of the invention has 55nm correlation length Ξ belowbRubber composition can be by the preparation that includes the following steps
Method preparation: kneading step (A), kneading step (B) and vulcanisation step.Kneading step (A) include by isoprene rubber with
Vulcanization accelerator is mediated.Kneading step (B) includes pinching the kneaded mixture obtained in kneading step (A) or later with sulphur
It closes.Vulcanisation step includes the unvulcanized rubber composition that vulcanization obtains in kneading step (B) or later.For adding other materials
The kneading step of material can before kneading step (A), between kneading step (A) and (B) or after kneading step (B)
It carries out.
In kneading step (A), it is preferable that the rubber components comprising isoprene rubber and vulcanization accelerator are 150
It is mediated under~250 DEG C of kneading temperature.In this case, the aggregation of vulcanization accelerator can be destroyed with free radical,
Vulcanization accelerator is bonded with rubber components, and therefore can be formed uniformly crosslinking starting in rubber composition
Point.Further, since isoprene rubber can generate 3 grades of stable free radicals in allylic positions, therefore in kneading step
(A) it is easy to form key with vulcanization accelerator in.In addition, in the conventional technology, since vulcanization accelerator is in polybutadiene rubber
(BR) or butadiene-styrene rubber (SBR) is middle than having higher solubility in isoprene rubber, therefore they can be limited in
In BR or SBR, therefore, it is difficult to form the structure of homogeneous cross-link.On the contrary, kneading step (A) can be used to eliminate vulcanization in the present invention
Localization of the promotor in BR or SBR, so as to form the structure of homogeneous cross-link.Due to above-mentioned effect, crosslinking is improved
The uniformity of structure, to obtain lesser correlation length Ξb.Therefore, rubber composition obtained shows low energy damage
Mistake, excellent energy to failure and excellent wearability.
Kneading temperature in the present invention refers to the maximum temperature in kneading process.As previously mentioned, in kneading step (A),
Kneading temperature can be set as 150 DEG C or more to reduce correlation length Ξb, and kneading temperature can be set as 250 DEG C or less with suppression
The thermal decomposition of rubber components processed and incipient scorch.In order to form the expected knot being more evenly crosslinked that can provide the performance further improved
Structure, kneading temperature are preferably 160 DEG C or more, more preferable 170 DEG C or more, but preferably 220 DEG C hereinafter, more preferable 200 DEG C hereinafter, more
It is preferred that 190 DEG C or less.Kneading temperature can be controlled for example, by addition filler or using temperature controller.
In preparing rubber composition of the invention, the kneading temperature in kneading step (A) must be not necessarily 150 DEG C with
On.In addition, kneading temperature, which is 150 DEG C or more, can not provide rubber composition of the invention.It, can in kneading step (A)
The duration is mediated to enhance dispersion of the vulcanization accelerator in rubber, to reduce correlation length Ξ to increaseb；Furthermore, it is possible to
Increase kneading temperature simultaneously.In addition, by using the masterbatch (vulcanization accelerator masterbatch) containing rubber components and vulcanization accelerator,
It can be further improved the dispersibility of vulcanization accelerator.It is, for example, less than total rubber component when isoprene rubber content is low
50 mass % when, correlation length ΞbIt is difficult to decrease.However, using above-mentioned technology, it can obtain to meet and limit in the present invention
Correlation length ΞbRubber composition.The following guidance for obtaining rubber composition of the present invention is provided: preferred kneading temperature with hold
The continuous time are as follows: for the rubber components of the isoprene rubber containing 80~100 mass %, be respectively higher than 150 DEG C and
10 minutes or more；For containing at least rubber components of 40 mass % but the isoprene rubber less than 80 mass %, difference
For higher than 160 DEG C and 15 minutes or more；For containing at least 20 mass % but less than the isoprene rubber of 40 mass %
Rubber components, respectively be higher than 170 DEG C and 15 minutes or more；For containing the isoprene rubber lower than 20 mass %
Rubber components, preferably kneading temperature and duration are adjusted to respectively higher than 170 DEG C and 15 minutes or more, at the same use sulphur
Change other rubber of promotor master batch form.
Therefore, the kneading duration in kneading step (A) is not particularly critical, can suitably be set in 1 to 60 point
In the range of clock.Kneading in kneading step (A) can also carry out in any way, for example, using known kneading machine such as class
Mixer, kneader or open mill in uncle.
Other rubber in addition to isoprene rubber can be introduced and mediated in kneading step (A).It can also be
It mediates in kneading step (A) commonly used in the material in rubber composition, such as zinc oxide, stearic acid, carbon black, silica, silicon
Alkane coupling agent, antioxidant, oil, wax and processing aid.However, sulphur does not preferably introduce during or before kneading step (A), and
It is to be mediated in kneading step (B), incipient scorch can be inhibited.Sulphur mentioned herein is the sulphur as the material commonly used in tire,
Such as powder sulphur, do not imply that the sulphur atom in vulcanization accelerator or silane coupling agent.In addition, inhibiting in kneading step (A)
The zinc oxide and stearic acid reacted between rubber components and vulcanization accelerator is preferably arrived in rubber components and vulcanization accelerator kneading
It introduces and mediates afterwards to a certain degree, preferably reach 150~250 DEG C after at least 1 minute in temperature.Alternatively, they preferably with pinch
It closes and is mediated in step (A) separated step, more preferably in kneading step (B).
Kneading step (B) includes that the kneaded mixture that will be obtained in kneading step (A) or later and sulphur are mediated.
Kneading step (B) is preferably included at 130 DEG C of temperature below and mediates.In the step separated with vulcanization accelerator
Sulphur is introduced and mediated at 130 DEG C of temperature below provides the effect for further suppressing incipient scorch.The lower limit of kneading temperature is preferably
70 DEG C, to improve the dispersion of sulphur.
The kneading duration in kneading step (B) is not particularly critical, but preferably 1~60 minute.Kneading step (B)
In kneading can also carry out in any way, for example, using known kneading machine such as Banbury mixer, kneader or mill
Machine.
In kneading step (B), the kneaded mixture and sulphur that will at least obtain in kneading step (A) or later are mediated,
Optionally, it is mediated together with other materials.As described above, it is preferred to mediate zinc oxide and stearic acid in kneading step (B).
Vulcanisation step includes the unvulcanized rubber composition that vulcanization obtains in kneading step (B) or later.
It can be with by the kneaded mixture (unvulcanized rubber composition) of the kneading step acquisition including kneading step (A) and (B)
Vulcanize by conventional method, to obtain vulcanized rubber composition.The condition of vulcanization is not particularly limited.Preferably, heating is 100
It is carried out 5~60 minutes at~180 DEG C.For tire production, unvulcanized rubber composition can be extruded into tyre element such as tyre surface
Shape, be then formed together and assemble with other tyre elements on tyre building machine in a usual manner, it is unvulcanized to construct
Tire (green tire), then the unvulcanized tire (green tire) can be heated and pressurizeed in vulcanizer.
Embodiment
Reference implementation example is specifically described into the present invention, but not limited to this.
It is listed below chemicals used in embodiment and comparative example.
Isoprene rubber (IR): the Nipol IR 2200 purchased from Nippon Zeon Co., Ltd.
BR: the Ubepol BR150B purchased from Ube Industries, Ltd
SBR: (rubber solids of every 100 mass parts contain 37.5 mass parts to the Tufdene 3830 purchased from Asahi Kasei Corporation
Oil)
Carbon black: the DIABLACK N550 (N purchased from Mitsubishi chemical Co., Ltd2SA:42m2/g)
Silica: purchased from the ULTRASIL VN3 for winning wound
Silane coupling agent: the NXT (3- Octanoylthio propyl-ethoxy silane) purchased from Momentive
Zinc oxide: the zinc oxide #1 purchased from Mitsu Mining & Smelting Co., Ltd
Stearic acid: the stearic acid " TSUBAKI " purchased from Japan Oil Co
Antioxidant: NOCRAC 6C (N- phenyl-N'- (the 1,3- dimethyl butyrate purchased from Ouchi Shinko Chemical Ind Co., Ltd.
Base) p-phenylenediamine, 6PPD)
Sulphur: the powder sulphur purchased from Qing Jingze sulphur Co., Ltd.
Vulcanization accelerator: NOCCELER CZ (the N- cyclohexyl -2-[4-morpholinodithio purchased from Ouchi Shinko Chemical Ind Co., Ltd.
Sulfenamide, CZ).
Vulcanization accelerator masterbatch: by the way that vulcanization accelerator (NOCCELER CZ) is added in NR latex and solidifies the mixture
To prepare (formula: vulcanization accelerator=100/2 NR/ (mass parts)).
<embodiment and comparative example>
(the first kneading step)
According to shown in table 1 to 8 respectively formula and kneading conditions, use Banbury mixer mediate rubber components and vulcanization promote
The total amount of agent.
(the second kneading step)
Using the Banbury mixer of 3L, under 100 DEG C of kneading temperature, the kneading obtained in the first kneading step is mixed
The total amount for the material listed in object and table 1 to 8 is mediated 15 minutes.
(third kneading step)
Using two-roll mill, under 100 DEG C of kneading temperature, the kneaded mixture and table that will be obtained in the second kneading step
The total amount for the material listed in 1 to 8 is mediated 5 minutes.
(vulcanisation step)
Using press machine, at 140 DEG C, the unvulcanized rubber composition obtained in third kneading step is heated 50 minutes,
To obtain vulcanized rubber composition.
As described below, the vulcanized rubber composition of above-mentioned preparation is evaluated.As a result it is provided in the lower part of table 1 to 8.
<SANS analysis>
The plaques (layered product) of thickness about 1mm, length about 16mm, width about 16mm are swelling to balance in deuterated toluene
And it is fixed on specimen holder.Then, neutron exposure sample is used at room temperature.With distance detector 2.5m, and is not using and making
It is strong to obtain absolute scatter with the range measurement sample of 10m, then being combined by least square method in the case where condenser lens
It writes music line.It combines this three curves in the following manner: the scattering that the fixed sample by measurement distance detector 2.5m obtains
Intensity curve, it is mobile to be measured and the scattering strength of acquisition at the distance of 10m without and with condenser lens
Curve.Pass through least square method, the scattering strength curve I being fitted, to determine correlation length Ξ using equation 1 to 6b。
(SANS device)
SANS equipment in SANS:SANS-J, it is the light of the JRR-3 of independent administrative corporation's Japan Atomic energy research and development organization
Bunch.
(analysis condition)
Neutron wavelength:
The flux density of neutron: 9.9 × 107Neutron/cm2/s
Distance of the sample to detector: 2.5m and 10m (sample is also measured at 10 meters of distance detector using condenser lens, with
Obtain the information of smaller angle.)
(detector)
Two-dimensional detector (3He two-dimensional detector and 2 D photoelectric multiplier tube+ZnS/6LiF detector)
<the tan δ index at 60 DEG C>
Using spectrometer (in Co., Ltd. island production manufactured by) with 1% dynamic strain amplitude, the frequency of 10Hz and 60 DEG C
Temperature measures tan δ.The inverse of tan δ value is expressed as index of the table 1 into table 8, and it is 100 that comparative example 1 to 8, which is set separately,.Index
Higher expression energy loss is fewer, it is believed that 100 or more index value is good.
<the energy to failure index at 25 DEG C>
Using autoplotter (Shimadzu Corporation), drawn with the rate of 200mm/min with No. 3 dumbbell shape punching presses
Rubber sample to be broken, with measure fracture when elasticity modulus (fracture tensile strength) and elongation (elongation at break).It surveys
Amount temperature is 25 DEG C.By the product of the two values divided by 2, quotient is defined as energy to failure.As a result it is expressed as finger of the table 1 into table 8
Number, it is 100 that comparative example 1 to 8, which is set separately,.Index is higher, and expression energy to failure is higher, it is believed that 100 or more index value is good.
<abrasion resistance index>
Using blue Berne abrasiometer, at room temperature, load 1.0kgf, slip rate 30% measures abrasion loss.Abrasion loss
Inverse be expressed as index of the table 1 into table 8, be set separately comparative example 1 to 8 be 100.Index is higher, and expression wearability is higher,
Think that 100 or more index value is good.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
As shown in table 1 to 8, with each compared with comparative example, in correlation length ΞbTo own in 55nm embodiment below
Performance is improved.Thus it is speculated that the not significant decrease of the performance as caused by the excessive thermal decomposition of rubber components.
In addition, when the scattering strength curve I obtained by SAXS analysis determines correlation length ΞbWhen, obtain similar result.
Claims (4)
1. a kind of rubber composition for tire, which is characterized in that the rubber composition includes:
Rubber components containing isoprene rubber,
The rubber composition has 55nm correlation length Ξ belowb, the correlation length ΞbIt is logical by being fitted with following formula 1 to 6
It crosses the scattering strength curve I (q) of X-ray scattering analysis or neutron scattering analysis acquisition and determines:
ξ < Ξb< Ξc(formula 2)
A=8 π Naσ2ξ3(formula 3)
A, B, C, ξ, Ξb, Ξc: fitting parameter
Q: Scattering of Vector
Na: per unit volume number (a/cm of the scatterer with correlation length ξ3)
Nb: there is correlation length ΞbScatterer per unit volume number (a/cm3)
Nc: there is correlation length ΞcScatterer per unit volume number (a/cm3)
σ: the poor (electronics (cm of electron density between scatterer and surrounding substrate-3)) or scatterer and surrounding deuterated solvent it
Between scattering length density contrast (cm-2)
θ: angle of scattering
λ: the wavelength of X-ray or neutron.
2. rubber composition for tire according to claim 1,
Wherein, the X-ray scattering analysis is small angle x-ray scattering (SAXS) analysis, and the neutron scattering analysis is low-angle neutron
Scattering analysis.
3. rubber composition for tire according to claim 1 or 2,
Wherein, the value of the q defined by formula 6 is 10nm-1Below.
4. a kind of tire comprising rubber composition for tire according to any one of claims 1 to 3.
Applications Claiming Priority (3)
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| JP2016232626 | 2016-11-30 | ||
| JP2016-232626 | 2016-11-30 | ||
| PCT/JP2017/042639 WO2018101266A1 (en) | 2016-11-30 | 2017-11-28 | Rubber composition for tire and tire |
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| CN109937236A true CN109937236A (en) | 2019-06-25 |
| CN109937236B CN109937236B (en) | 2022-08-16 |
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| US (1) | US11242448B2 (en) |
| EP (1) | EP3549978B1 (en) |
| JP (1) | JP7070399B2 (en) |
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| CN114174401A (en) * | 2019-07-22 | 2022-03-11 | 大陆轮胎德国有限公司 | Sulfur-crosslinked rubber mixture and vehicle tire |
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| JP7070399B2 (en) * | 2016-11-30 | 2022-05-18 | 住友ゴム工業株式会社 | Rubber composition for tires and tires |
| JP7069564B2 (en) * | 2017-04-25 | 2022-05-18 | 住友ゴム工業株式会社 | Rubber composition for tires, manufacturing method of rubber composition for tires and tires |
| JP6939953B1 (en) * | 2020-06-15 | 2021-09-22 | 住友ゴム工業株式会社 | Tire and rubber composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20190315946A1 (en) | 2019-10-17 |
| CN109937236B (en) | 2022-08-16 |
| EP3549978A1 (en) | 2019-10-09 |
| JP7070399B2 (en) | 2022-05-18 |
| JPWO2018101266A1 (en) | 2019-10-24 |
| US11242448B2 (en) | 2022-02-08 |
| WO2018101266A1 (en) | 2018-06-07 |
| EP3549978B1 (en) | 2023-05-10 |
| EP3549978A4 (en) | 2020-07-29 |
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